Polyorganosiloxanes having alkoxylated side chains

ABSTRACT

Described are polysiloxane compositions that are obtainable in 2 steps. The first step comprises reacting a linear organopolysiloxane which contains Si—H bonds with a compound that has a terminal C═C double bond and a polyoxyalkylene chain. This reaction is carried out in such a way that Si—H bonds are still present in the resultant product. The second step comprises adding a base or water and an acid to the resultant product. The hydrophilic properties of the resultant polysiloxane compositions can be influenced in a specific manner. The compositions are useful for treating fiber materials, especially textile fabrics. The effects obtained are notable for good durability. Further groups may be incorporated into the polysiloxanes to open up further applications.

[0001] This invention relates to specific organopolysiloxanecompositions and to their use for treating fiber materials, especiallytextile fabrics in the form of wovens, knits or nonwovens.

[0002] It is known to treat textile fabrics with compositions whichinclude polysiloxanes to control textile water repellency,hydrophilicity and hand, depending on the choice of polysiloxane. Thecompositions usually used for this purpose are aqueous solutions ordispersions which include the desired polysiloxanes. A particularly softhand is obtainable when the organopolysiloxanes have side chains thatcontain amino groups.

[0003] Textile fabrics have also been treated using organopolysiloxaneswhich contain polyoxyethylene groups with or without polyoxypropylenegroups. Such polysiloxanes and their use are described in EP 578 144 A2,DE-A 26 07 469, DE-B 39 28 867, EP 494 683 A1 and WO 99/47111.

[0004] Textile fabrics have also been treated using polysiloxanes havingSi—OH bonds, for example α,ω-dihydroxypolydimethylsiloxanes, alsopolysiloxanes containing Si—H bonds, for example polyalkylhydrosiloxanesas described in Ullmanns Encyklopädie der technischen Chemie, 4thedition, Volume 23,1983, page 82/83, Verlag Chemie, Weinheim, Germany.The use of hydropolysiloxanes is also disclosed in GB-A 2 082 215.Polysiloxanes containing Si—H bonds and their use are also described inEP-A 755 960 and EP-A 755 961.

[0005] Although prior art silicone textile finishes have someadvantages, they are not in every respect optimal. For instance, in manycases it is not possible to control the hydrophilic properties of thefinished fiber materials with these known polysiloxanes in a specificmanner. Another problem is the frequently inadequate durability of theeffects, especially after the textile has been washed.

[0006] It is an object of the present invention to provide polysiloxanecompositions which confer a pleasantly soft hand on fiber materialstreated therewith and which also make it possible to influence thehydrophilic/hydrophobic properties of fiber materials in a specificmanner and which lead to excellent durability for the effects mentioned.

[0007] This object is achieved by a polysiloxane composition preparableby reacting a linear organopolysiloxane whose chain ends are formed byR₃SiO— units and which has on average two or more —Si(R)(H)—O— units inthe chain with a compound of the formula (I)

CH₂═C(R¹)CH₂_(m)—OCH₂CH₂O_(x)CHR²—CHR³—O_(y)CH₂₄—O_(z)R¹  (I)

[0008] where the individual —CH₂CH₂O—, —CHR²—CHR³—O— and (CH₂)₄—O unitsmay be distributed in the chain of the compound of the formula (I) inany desired pattern, this reaction being carried out in such a way thatthe resultant product still contains Si—H bonds and the resultantproduct is admixed with water or a protic acid or a base, the base beingan amino-functional organopolysiloxane or a mixture of an alcohol of 5to 50 carbon atoms and an alkali metal alkoxide or a mixture of waterand a strong inorganic base, wherein every R is independently phenyl oralkyl of 1 to 4 carbon atoms, R¹ is H or R, one of R² and R³ is H andthe other is CH₃ and wherein

[0009] m is from 1 to 8, preferably 1,

[0010] x is from 2 to 40,

[0011] y is from 0 to 10, and

[0012] z is from 0 to 10.

[0013] The compositions of the invention are very useful for treatingfiber materials, especially textile and fabrics in the form of wovens,knits or nonwovens. For this they are preferably used in the form ofaqueous dispersions or solutions and can be applied to these fabrics inthe course of the textile finishing process, for example after a dyeingstep, using known methods, for example by padding. The fabrics can becomposed of a variety of materials such as wool, cotton, regeneratedcellulose or synthetics such as polyester or polyamide. Similarly,textile fabrics composed of blends of fibers, for example fibers of thetype mentioned, can be treated with compositions according to theinvention. The finishing liquors here may include further customarytextile finishing additives, for example flame retardants or cellulosecrosslinkers.

[0014] By choosing compositions according to the invention in a specificmanner, the hydrophilic/hydrophobic properties of the fiber materialstreated can be influenced in a specific manner. For instance, raisingthe degree of ethoxylation (=raising the value of x in the compounds offormula (I)) imparts enhanced hydrophilicity to the fiber materials.When x, y and z in formula (I) have suitable values it is possible toobtain compounds according to the invention that are self-dispersing orsoluble in water without use of dispersants. Compounds according to theinvention may frequently even function efficiently as dispersants fordispersing other products in water or in oil, ie. for preparing O/W orW/O emulsions, including for cosmetic purposes. Compounds according tothe invention confer on textile fabrics, for example garments, apleasant, very soft hand even without the presence of amino groups orwithout the additional use of soft-hand agents. If desired, however,soft-hand agents of the type customary in the textile finishing industrymay be used in addition.

[0015] The effects provided by compositions according to the inventionpossess good durability, even after the textiles have been washed. Apossible explanation is that the compositions contain Si—H bonds orSi—OH bonds and so are crosslinkable with themselves or with the fibermaterial, for example in the case of the use of a customary cellulosecrosslinker, or else that a crosslinking reaction has taken place evenbefore the application to the fiber material, for example because anamino-functional polysiloxane has been used as a base in the synthesis.These matters will be discussed hereinbelow.

[0016] Compounds according to the invention are obtainable by firstreacting a linear organopolysiloxane of the hereinbelow described typewith a compound of the formula (I) and subsequently adding water andacid or a base of the hereinbelow designated type. Theorganopolysiloxane used for the reaction mentioned is linear, ie. allthe silicon atoms it contains are situated in a single polymer chain.This chain preferably contains 10 to 500 silicon atoms. The ends of thischain are formed by R₃Si—O— units. Every R is independently a phenylradical or a linear or branched alkyl radical of 1 to 4 carbon atoms.Preferably R is methyl. This applies not only to the chain ends, butalso to the other R-containing groups in the polysiloxanes used.Similarly, in the compounds of the formula (I) R is preferably CH₃ whenR¹═R.

[0017] The polysiloxane chain in the linear organopolysiloxanes used asa starting compound shall contain at least two —Si(R)(H)—O— units onaverage. It may also contain more such units. These units contain anSi—H bond as well as an Si—R bond. This Si—H bond is reactive andcapable of crosslinking, condensation and addition reactions. When thepolysiloxanes are reacted with compounds of the formula (I), an Si—Hunit is added to the C═C double bond of a compound of the formula (I).

[0018] The statement made above and in claim 1, that theorganopolysiloxane used shall on average contain two or more—Si(R)(H)—O— units, means the following: polymer syntheses will forknown reasons virtually always give rise to mixtures of products thatdiffer in chain length among other respects. It is therefore possiblethat some molecules of the organopolysiloxanes which can be used forpreparing compositions according to the invention contain only one or nounit of the formula —Si(R)(H)—O—. However, the majority of the moleculesshall contain at least two such units and on average theorganopolysiloxane used shall contain two or more such units, ie. thetotal number of such units present has to be at least 2 n, where n isthe number of molecules of the organopolysiloxane. Preferably, 20 to100% of the silicon atoms in the organopolysiloxane used for thereaction, except for the two silicon atoms at the chain ends, each havea hydrogen atom attached to them.

[0019] As well as the —Si(R)(H)—O— units mentioned, theorganopolysiloxane chain may contain further units; in a preferredembodiment it additionally contains —Si(R₂)O— units, where R is asdefined above and in claim 1. In a further preferred embodiment, unitsof the formula —Si(R)(R⁴)—O— are still present in the chain. Here R isas defined above and R⁴ is linear or branched alkyl of 5 to 25 carbonatoms. The polysiloxane chain may also contain a plurality of such unitswhich differ in the chain length of the R⁴ radical. The presence oflonger-chained alkyl R⁴ radicals may be responsible for even furthersoftening of the hand of the finished fiber materials.

[0020] The reaction with a compound of formula (I) may be carried outnot only with a single organopolysiloxane but also with a mixture oforganopolysiloxanes which meet the abovementioned conditions. Similarly,instead of a single compound of the formula (I) being used it is alsopossible to use a mixture of such compounds, for example a mixture whichincludes two compounds of formula (I) of which one contains—CHR²—CHR³—O— and/or (CH₂)₄—O— units (y and/or z>0) and the otherdoesn't (y=0, z=0). Mixtures whose individual products differ in thevalue of x are also useful.

[0021] Organopolysiloxanes useful as starting materials for the reactionwith compounds of the formula (I) are commercially available, forexample products from Wacker Chemie GmbH, Germany.

[0022] Compounds of the formula (I) are ethoxylated orethoxylated/propoxylated alcohols which may additionally contain(CH₂)₄—O— butoxy groups. The R¹ radical present on the second carbonatom of the C═C double bond is hydrogen or an R radical of the typedescribed above. This R¹ is preferably hydrogen. When R¹ is R, it ispreferably a methyl group. The other R¹ radical present in the formula(I), namely the R¹ radical at the end of the polyoxyethylene orpolyoxyethylene/polyoxypropylene/polyoxybutylene chain is likewisehydrogen or an R radical. This R¹ radical is preferably methyl.

[0023] In the formula (I) m is from 1 to 8, preferably 1. In the lattercase, the compounds of the formula (I) are preferably alkoxylated(meth)allyl alcohols. They are preparable by ethoxylation and/orethoxylation/propoxylation with or without butoxylation of (meth)allylalcohol in a conventional manner and optionally subsequentetherification of the terminal OH group. When it is not just anethoxylation but also a propoxylation (y>0) which is being carried out,the ethoxylation and propoxylation may be carried out simultaneously orin succession. The former gives rise to random copolymers, the latter toblock copolymers. Consequently, in the formula (I) the individual—CH₂CH₂—O—, CHR²—CHR³—O— and (CH₂)₄—O— units need not be arrangedprecisely as expressed by formula (I), but may be distributed in thechain in any pattern. In the formula (I) one of R² and R³ is hydrogenand the other is methyl. The units of the formula CHR²—CHR³—O— areformed in a known manner by reaction of a terminal OH group withpropylene oxide. The introduction of butoxy groups (CH₂)₄—O— is effectedin a known manner by reacting the allyl alcohols or the previouslyethoxylated or ethoxylate/propoxylated allyl alcohols withtetrahydrofuran in the presence of ethylene oxide and/or propylene oxideand by using an acidic catalyst.

[0024] In the formula (I), x is from 2 to 40, preferably from 5 to 30, yis from 0 to 10, preferably from 0 to 8, and z is from 0 to 10,preferably from 0 to 8. Preference is given to using compounds of theformula (I) where x is not less than the sum total of y and z. Thevalues of x, y and z are specifically controllable in a known manner bymeans of the quantitative ratios used for the alkoxylation. Sincealkoxylations normally give rise to mixtures of compounds of differentvalues of x and/or y and/or z, compositions according to the inventionare customarily prepared using such mixtures of compounds of the formula(I).

[0025] Useful compounds of the formula (I) are obtainable on the market,for example Pluriol A 010 R (BASF AG, Germany).

[0026] The reaction of organopolysiloxane with a compound of the formula(I) is customarily carried out at a temperature in the range from 40 to130° C., preferably 80-110° C., and can be carried out without use of asolvent. A catalyst or a mixture of catalysts can be used for thisreaction. Useful catalysts include metal compounds, especially salts orcomplexes of rhodium, of palladium or of platinum such as H₂PtCl₆ or1,3-divinyl-1,1,3,3-tetramethyldisiloxaneplatinum(0) complex (thiscomplex is obtainable in the form of a concentrate from Degussa-Hüls,Germany). Preferably the organopolysiloxane and a portion of thecompound of the formula (I) are initially charged and the rest of thecompound of the formula (I) and the catalyst are gradually added to thisinitial charge.

[0027] The reaction of the organopolysiloxane with a compound of theformula (I) has to be carried out in such a way that the resultantproduct still contains Si—H bonds. These are capable of furtherreactions, for example for a subsequent reaction with water and acid orwith base. In order that the resultant product may still contain Si—Hgroups, the reaction is carried out using a deficiency of C═C doublebonds compared to the Si—H bonds present. However, in certaincircumstances, for example when the reaction does not go to completionfor steric reasons, the resultant product will still have Si—H bondswhen the amounts of C═C used are equivalent to the amounts of Si—H used.Before equivalent quantities are used, however, a preliminary testshould be carried out to examine whether the reaction product stillcontains Si—H bonds. In the event that the reaction does not go tocompletion, for example for steric reasons, the resultant product willstill include fractions of compound of the formula (I). These mayinterfere with the further reaction with acid or base or with the use ofthe compositions according to the invention. In such a case, they haveto be removed beforehand. In the event of a sterically hinderedreaction, it can be advisable to use equivalent amounts of C═C doublebonds, based on Si—H bonds, in order that the desired number ofalkoxylates be incorporated into the polysiloxane. Where an excess levelof compounds of formula (I) is not troublesome in the products obtainedafter the reaction of the organosiloxane with a compound of formula (I),it can be advantageous to carry out the reaction with an excess of C═Cdouble bonds of the compound of formula (I) compared to Si—H bonds ofthe organopolysiloxane, under the precondition, of course, that not allthe Si—H bonds of the siloxane are converted. With this procedure, thecompositions according to the invention will still include fractions ofunconverted compounds of the formula (I) and they are particularlyuseful as emulsifiers. Another way of preparing such emulsifiers is toprepare compounds according to the invention without excess of compoundof the formula (I) and subsequently to add once more certain amounts ofcompounds of the formula (I). In a preferred embodiment, the reaction iscarried out with such amounts of organopolysiloxane that a total of 0.7to 1.0 C═C double bonds in the compound of the formula (I) are used perSi—H bond. When the organopolysiloxane is additionally reacted with acompound of the formula (II) before, during or after the reaction of thecompound of the formula (I), the same statement applies mutatismutandis. In this case the stated 0.7 to 1.0 C═C double bonds is basedon the sum total of the C═C double bonds present in the compound of theformula (I) and of the formula (II).

[0028] After the reaction of the organopolysiloxane with the compound ofthe formula (I), the resultant product is mixed with a base or water ora protic acid, preferably a strong acid. When water and a protic acidare used, the Si—H bonds still present in this product will react toform Si—OH bonds. Protic acids here are Brönsted acids, which are eitherused as such or released from Lewis acids in the presence of water. Theresultant Si—OH bonds are capable of further reactions, for examplecrosslinking with textile fiber material. An example of this iscrosslinking by reaction with OH groups of cellulose material.Similarly, crosslinking with reaction groups generated by a precedingplasma treatment of the textile material is a possibility. Such a plasmatreatment can be effected according to known methods, one of thesemethods being a pretreatment of the textile material with oxygen plasmaunder reduced pressure. Fiber materials useful for such a plasmatreatment include cellulose, regenerated cellulose, wool and polyamide.

[0029] The Si—OH bonds formed are accessible not only to thecrosslinking reactions mentioned but also to condensation reactions, forexample with silanes and polysiloxanes. This is described hereinbelow.

[0030] To add water and an acid, preferably a strong acid, to theproduct which has formed after the reaction of the organopolysiloxanewith the compound of the formula (I), it is preferable to pour thisproduct into water and then to slowly add an aqueous solution of theacid. The resulting exothermic reaction, which releases hydrogen, shouldbe controlled by monitoring the temperature in the reaction vessel.Useful acids include strong mineral acids such as sulfuric acid,hydrochloric acid, phosphoric acid or acetic acid or formic acid. It isadvantageous for the mixture of water and acid and reaction product tohave a pH in the range from 0.5 to 4.5. After the reaction of the Si—Hbonds and before use of the inventive composition for textile treatment,the acid should be at least partially neutralized in order that damageto the textile fiber material may be avoided.

[0031] Instead of water and acid, a base may also be added to thereaction product of organopolysiloxane and the compound of the formula(I). The use of base is preferable to the use of acid. This base can beamino-functional organopolysiloxane, a mixture of water and stronginorganic base or a mixture of alcohol of 5 to 40 carbon atoms and analkali metal alkoxide. The base may be added at room temperature or atslightly elevated temperature. When an amino-functionalorganopolysiloxane is used, it is believed that the amino groups of thispolysiloxane will react with the Si—H bonds of the reaction product byevolving hydrogen and forming Si-N bonds. The products thus formedalready have a certain degree of crosslinking, which provides gooddurability for the effects after application to fiber materials. Byusing a deficiency of amino groups in the amino-functional polysiloxanethe resultant product will still contain Si—H bonds capable ofcrosslinking with reactive groups of the fiber material, especially atelevated temperatures.

[0032] Useful amino-functional polysiloxanes include for examplepolydimethylsiloxanes in which one or more non-terminal methyl groupsare each replaced by a radical containing one or more amino groups. Suchproducts are commercially available, for example from Dow Corning orWacker GmbH. They are preparable by a known equilibration of linear orcyclic siloxanes in the presence of silanes which contain two alkoxyradicals and one amino-functional radical attached to silicon.Similarly, radicals having sterically hindered amino-functional radicalsare suitable, as described for example in EP-A 659 930. Further suitableamino-functional polysiloxanes are disclosed in U.S. Pat. No. 5,310,783.

[0033] In place of amino-functional polysiloxane, a mixture of analcohol of 5 to 50 carbon atoms and an alkali metal alkoxide may be usedas base. The alkali metal alkoxide, which serves as a catalyst, ispreferably sodium methoxide, potassium methoxide, sodium ethoxide orpotassium ethoxide. As described above for the case of the addition ofwater and acid, the procedure employed is preferably similar in that theresultant reaction product is combined with a portion of the alcohol andthen, while monitoring the temperature, the rest of the alcohol and thealkoxide are gradually added. As the alcohol and alkoxide are added tothe product of the reaction mentioned, the Si—H bonds are converted intoSi—O-C bonds. The amount of alkoxide can be in the customary range knownfor catalysts. It should be determined in such a way that the pH of themixture is in the range from about 7.5 to 10.5. The amount of alcoholadded is advantageously determined in such a way that the number of OHgroups of the alcohol which react with Si—H is approximately equivalentto the number of Si—H bonds, so that essentially all the Si—H bonds areconverted into Si—O-C bonds. The alcohol used contains 5 to 50 carbonatoms. It can be monohydric or polyhydric alcohol wherein the individualhydroxyl groups are attached to a linear or branched monovalent orpolyvalent hydrocarbyl radical. A portion of the hydrogen atoms of thishydrocarbyl radical may be substituted by fluorine atoms. Usefulalcohols include for example alcohols whose hydrocarbyl radicals areperfluoroalkyl groups. A useful polyhydric alcohol is

C(CH₂OH)₂[CH₂X_(t)(CH₂)_(u)—R_(F)]₂

[0034] where

[0035] X is —O— or —S—,

[0036] R_(F) is a perfluoroalkyl radical of 2 to 20 carbon atoms,

[0037] t is 0 or 1 and

[0038] u is from 1 to 4. Such alcohols are described in U.S. Pat. No.5,214,121 and U.S. Pat. No. 4,898,981. It is also possible to usealcohols of the formulae

HOCH₂_(w1)R_(F) and HOCH₂_(w2)CH₃

[0039] where R_(F) is as defined above, w1 is from 0 to 10 and w2 isfrom 4 to 20, or alcohols of these formulae wherein one or more hydrogenatoms of the —CH₂— groups are replaced by OH. The base added after thereaction of the organopolysiloxane with a compound of the formula (I)may also be a mixture of water and a strong inorganic base. The use ofsuch a mixture is preferable to the use of another base and to the useof water and acid. Preferred strong inorganic bases are sodium hydroxideor potassium hydroxide. Similarly to the method described above,preferably at first only a portion of the desired amount of water isadded to the reaction product. Subsequently the rest of the water andthe strong inorganic base are then added, advantageously in the form ofan aqueous solution of this base. The addition of the strong inorganicbase should take place while monitoring the temperature of the reactionmixture, since the ensuing reaction is exothermic and evolves H₂. Thisreaction converts the Si—H bonds of the reaction product used into Si—OHbonds. These are capable of further reactions, for example crosslinkingwith reactive groups of the textile fiber material at elevatedtemperature. Such crosslinking, for example with OH groups on cellulosematerials, provides excellent durability for the effects provided by thecompositions according to the invention. Another way in which the Si—OHgroups formed may further react is in crosslinking or condensationreactions even before application to fiber materials. This is describedhereinbelow.

[0040] Like the alkoxide in the case of the aforementioned use of amixture of alcohol and alkoxide, the strong inorganic base which is usedin the mixture with water performs the function of a catalyst. Theamounts of strong inorganic base used can accordingly be in the rangecustomary for catalysts. Preferably the reaction mixture has a pH ofabout 7.5 to 10.5 after addition of water and strong inorganic base. Asin the case of the addition of acid it can be advisable to neutralizethe mixture again after the Si—H bonds have been converted. The amountof water used in the case of the use of a mixture of water and a stronginorganic base is preferably at least such that substantially all Si—Hbonds are converted into Si—OH bonds. In some cases more water can beused, for example when the resultant compositions according to theinvention are subsequently to be converted directly into aqueousdispersions of these compositions. In other cases, in contrast, a largeexcess of water is to be avoided, for example when an equilibration orcondensation reaction is to be carried out subsequently, as describedhereinbelow, only just enough water or slightly more should be used asis needed to convert the Si—H bonds into Si—OH bonds and to hydrolyzethe Si—OR groups of the aminodialkoxyalkylsilane.

[0041] In addition to using a mixture of an alcohol containingperfluoroalkyl groups and alkoxide as a base there are other ways tointegrate perfluorinated R_(F) radicals into compositions according tothe invention. The compositions obtained as a result are frequentlyuseful for purposes for which compositions according to the inventionthat contain no fluorine are less appropriate. A possible use forinventive compositions containing perfluoroalkyl radicals is infirefighting, for example by applying such a composition to burningcarpets of oil. It is advantageous for this purpose to use suchcompositions as possess an enhanced hydrophilicity owing to their highlevel of CH₂CH₂O— units and as may be useful as dispersants forinterfacial boundaries. When such applications are contemplated, thereis a preferred embodiment of compositions according to the inventionwherein the organopolysiloxane used is reacted with a compound of theformula (II) before or simultaneously with the reaction with thecompound of the formula (I), or, after the reaction of theorganopolysiloxane with the compound of formula (I), the resultantproduct is reacted with a compound of formula (II) prior to addition ofwater and acid or base, this reaction with a compound of formula (II)being carried out in such a way that the resultant product stillcontains Si—H bonds,

CH₂═C(R¹)—R⁵—X_(b)—R⁶—R_(F)  (11)

[0042] where

[0043] R_(F) is a linear or branched perfluoroalkyl radical of 2 to 20carbon atoms,

[0044] X is —O—, —S—, —S—S—, —NR¹—SO₂—, —NR¹—, —NH—CO—O—, —NH—CO—NH—,O—CO— or —CO—O—,

[0045] R⁶ is CH₂₆, where a is from 0 to 10,

[0046] R⁵ is R⁶ or an R⁶ radical where a is from 1 to 10 and in which ahydrogen atom is replaced by —X_(b)—R⁶—R_(F) or by —COOH,

[0047] b is 0 or 1, and

[0048] R¹ is as defined in claim 1.

[0049] In similar fashion to their reaction with the C═C double bonds ofthe formula (I), Si—H bonds of the organopolysiloxane may also add toC═C double bonds of the formula (II) to provide organopolysiloxanescontaining R_(F) perfluoroalkyl radicals. The reaction can be carriedout by reacting the organopolysiloxane with a compound of the formula(II) before or simultaneously with the reaction with a compound of theformula (I). In both cases care must be taken to ensure to use only suchamounts of compound of the formula (II) that there are still Si—H bondsin the organopolysiloxane which are capable of reacting with thecompound of the formula (I). It is preferable to use a compound or amixture of compounds of the formula (II) in such amounts that 0 to 0.6C═C double bonds of the formula (II) are used per C═C double bond of theformula (I). In place of a single compound of the formula (II) it isalso possible to use a mixture of such compounds. The reaction with acompound of the formula (II) can also take place after the reaction ofthe organopolysiloxane with a compound of the formula (I), but beforethe addition of base or of water and acid. The reaction with a compoundof the formula (II), like the reaction with a compound of the formula(I), can be carried out in the presence of a catalyst. Useful catalystsinclude the same metal-containing catalysts as described for thereaction with a compound of the formula (I). Regardless of the time atwhich the reaction with a compound of the formula (II) is carried out,care must be taken to ensure that the resultant product still containsSi—H bonds before base or water and acid are added. This is controllablethrough choice of suitable quantitative ratios.

[0050] In the formula (II) R_(F) is a perfluoroalkyl radical which maybe linear or branched and contains 2 to 20 carbon atoms. This radical ispreferably unbranched. The R₁ radical is as defined above and in claim 1and preferably is hydrogen or methyl. The divalent X radical is oxygen,sulfur, a disulfide linkage,

[0051] —NR¹—, —NR¹—SO₂—, —NH—CO—O—, —NH—CO—NH—, —O—CO— or —CO—O—. R¹here is again as defined above. When X is —NR¹—SO₂— or —NH—CO—O—, thisradical is attached to the divalent R⁶ radical either via the nitrogenatom or via an oxygen atom. In the formula (II) b is 0 or 1. R⁶ isCH₂₆, where a is from 0 to 10. The divalent R⁵ radical is eitherCH₂₆, where a is again from 0 to 10, or a radical that differs fromthe R⁶ radical in that a is from 1 to 10 and a hydrogen atom in the unitCH₂₆ is replaced by a radical of the formula —X_(b)—R⁶—R_(F) or by—COOH. Here X, b, R⁶ and R_(F) are each as defined above.

[0052] Compounds of the formula (II) are commercially available orpreparable by methods known to the chemist.

[0053] After, as described, a base or water and acid has been added tothe reaction mixture, polysiloxane compositions according to theinvention are present. These are useful for treating fiber materials inthe form of textile fabrics. For this purpose they are preferablyconverted into aqueous dispersions as described hereinbelow. Thesedispersions may have added to them further components of the type knownfor textile finishing, for example flame retardants and cellulosecrosslinkers.

[0054] Instead of being directly used for the treatment of fibermaterials, compositions according to the invention may be subjected tofurther chemical modifications prior to this use. An example of afurther chemical modification is the known equilibration ofpolysiloxanes by reacting a polysiloxane in the presence of an alkalinecatalyst with a silane in which at least two —OR radicals are attachedto the silicon atom. The other two radicals attached to silicon aresubstantially freely choosable. In this equilibration, which ispreferably carried out at a temperature in the range from 110 to 130°C., the chain of the polysiloxane is fragmented, the silane unit isincorporated and the chain is reformed. Catalysts useful for thispurpose include NaOH or KOH. This equilibration may be accompanied by asimilarly known condensation reaction to chain extend the polysiloxane.To this end, the polysiloxane is reacted in the presence of a catalystnot just with silane but with a mixture which includes silane and eithera linear α,ω-dihydroxypolyorganosiloxane or a cyclicoligodialkylsiloxane. There is accordingly a preferred embodiment ofcompositions according to the invention wherein the product obtainedafter the addition of base or of water and acid is reacted with anaminodialkoxyalkylsilane or with a mixture which includes such a silaneand either a linear α,ω-dihydroxypolyorganosiloxane or a cyclicoligodialkylsiloxane. This reaction, which involves at least oneaminodialkoxyalkylsilane, has to be carried out in the presence ofwater. Useful linear dihydroxypolyorganosiloxanes have an OH group ateach chain end and may be widely varied in the chain length, for examplebetween 5 and 1000 silicon atoms. Useful cyclic oligodialkylsiloxanesinclude in particular hexamethylcyclotrisiloxane oroctamethylcyclotetrasiloxane. The equilibration/condensation reactionmay also be carried out using a mixture which, as well as silane,includes not just one of the two compounds mentioned here, but bothtogether.

[0055] The preferred silane for the equilibration or condensation is anaminodialkoxyalkylsilane of the following structure:

Si(R)(OR)₂(T)

[0056] where R is as defined above and in claim 1 and all R radicals areeach preferably independently methyl or ethyl. The T radical is amonovalent radical that contains one or more amino groups. Preferably itcontains at least one primary amino group. Useful T radicals aredisclosed in U.S. Pat. No. 5,612,409, where they are referred to as“radicals Z”.

[0057] This equilibration reaction provides compositions according tothe invention that comprise polysiloxanes containing one or more Tradicals and hence amino groups.

[0058] When using compositions according to the invention to treat fibermaterials, they are preferably used in the form of aqueous solutions oraqueous dispersions. Accordingly, in a preferred embodiment of thecompositions, the addition of base or of water and acid is followed bythe addition of water and optionally also a dispersant or dispersantmixture in such an amount that an aqueous polysiloxane dispersion isformed. A possible procedure in this case is to follow the reaction ofthe organopolysiloxane with the compound of the formula (I) by addingwater and an acid or an aqueous solution of an inorganic base in suchamounts that an aqueous dispersion is formed. This may necessitate ahomogenizing step and/or the use of one or more dispersants. The aqueousdispersion may also be prepared by stirring the product obtained afteraddition of acid or base into water with or without homogenization anduse of a dispersant. When, as described above, a reaction with acompound of the formula (II) or an equilibration or condensation usingan aminodialkoxyalkylsilane is carried out, the aqueous dispersion ispreferably not prepared until after these reaction steps.

[0059] When compositions according to the invention are not watersoluble or self-dispersing, one or more dispersants are used to prepareaqueous dispersions. Useful dispersants for this purpose includedispersants known to one skilled in the art of silicone emulsions, forexample ethoxylated fatty alcohols. When compositions according to theinvention contain perfluoroalkyl groups, cationic dispersants such asquaternized ammonium salts will frequently provide good results.

[0060] Depending on the ingredients of compositions according to theinvention, these are also obtainable in the form of particularly stablemicroemulsions. A suitable process for preparing microemulsions isdescribed in U.S. Pat. No. 5,057,572 for the case of amino-functionalpolysiloxanes. Polysiloxane microemulsions can be used for petroleumproduction as well as textile finishing.

[0061] The most important use of compositions according to the inventionis to use them in the form of aqueous dispersions for treating fibermaterials. Useful fiber materials include textile fabrics in particular.The compositions may be applied to these fabrics in a conventionalmanner, for example using a pad-mangle. The liquor concentrations usedhere may lie in the customary range, in which case the liquors mayinclude further known textile finishing components. After padding, thetextile is dried in a known manner and if necessary cured at elevatedtemperature. A cure, for example at 140-180° C., shall be carried out inparticular when crosslinking is desired for the composition of theinvention with itself or with the fiber material.

[0062] The examples which follow illustrate the invention.

EXAMPLE 1 (INVENTIVE)

[0063] 15 g of a commercially available alkylhydropolysiloxane whichcontains about 40 silicon atoms, has (CH₃)₃Si radicals at both chainends and contains —Si(CH₃(H)—O— units in the chain were reacted with 95g of an ethoxylated allyl alcohol (about 7—CH₂CH₂—O— units) whose chainend was formed by O-alkyl. The reaction, featuring approximatelyequivalent amounts of C═C double bonds and Si—H bonds, was carried outat about 100° C.-110° C. and in the presence of 18 ppm of platinum inthe form of H₂PtCl₆ as catalyst. The viscosity increased markedly duringthe reaction, which had ended after about 4 hours, providing a yellowishclear product having a viscosity of about 10 000 mpas.

[0064] 50 g of a product prepared as above were stirred into 150 g ofwater at room temperature. 0.3 g of 45% aqueous KOH was added withstirring. The mixture had a pH of about 9.5 and was stirred at roomtemperature for about 90 minutes and then adjusted to about pH 5 withacetic acid to provide a slightly yellowish clear product possessingexcellent utility for treating textile fabrics.

EXAMPLE 2

[0065] 15 g of the alkylhydropolysiloxane described in Example 1 wereinitially charged together with 3 g of 1-octadecene. A mixture of 90 gof an ethoxylated allyl alcohol (about 7—CH₂—CH₂—O— units) whose chainend was formed by —O-alkyl and 18 ppm of platinum in the form of H₂PtCl₆were added a little at a time under nitrogen. The exothermic reactioncaused the temperature to rise to 110° C. This was followed by asupplementary reaction at 110° C. for 3.5 h to provide a yellowish clearproduct having a viscosity of about 800 mpas.

[0066] 50 g of a product prepared as above were stirred into 150 g ofwater at room temperature, adjusted to pH 9-10 with 45% aqueous KOH andstirred at room temperture for 90 minutes. The pH was then adjusted toabout 5 with acetic acid.

EXAMPLE (COMPARATIVE)

[0067] 50 g of a linear organopolysiloxane which contained about 35silicon atoms, whose chain ends were formed by (CH₃)₃Si radicals andwhich contained approximately equal amounts of —Si(CH₃)₂—O— units and—Si(CH₃)=[CH₂CH₂CH₂—O—(EO)₆—H]—O— units in the chain but incontradistinction to products of the invention had no —Si(CH₃)(OH)—O—and no Si—H or other functional units were stirred into 150 g of waterat room temperature to provide a colorless clear, liquid product.

[0068] EO represents (CH₂CH₂—O)

[0069] Application Testing

[0070] Products obtained as per Example 1, Example 2 and the ComparativeExample were used to prepare aqueous liquors having a customaryconcentration of 30 g/l. To test the hand performance, cotton batistefabrics were padded with this liquor, while cotton-polyester knit wasused for the hydrophilicity test. The padded fabrics were dried at 110°C. for 10 minutes. Hydrophilicity Wetting time in [s] Soft hand *Example 1 0 2 Example 2 0 1 Comparative 0 3 Example

What is claimed is:
 1. A polysiloxane composition preparable by reactinga linear organopolysiloxane whose chain ends are formed by R₃SiO— unitsand which has on average two or more —Si(R)(H)—O— units in the chainwith a compound of the formula (I) CH₂═C(R¹)CH₂_(m)—OCH₂CH₂O_(x)CHR²—CHR³—O _(y)CH₂—O_(z)R¹  (I) where the individual—CH₂CH₂O—, —CHR²—CHR³—O— and (CH₂)₄—O units may be distributed in thechain of the compound of the formula (I) in any desired pattern, thisreaction being carried out in such a way that the resultant productstill contains Si—H bonds and the resultant product is admixed withwater and a protic acid or is admixed with a base, the base being anamino-functional organopolysiloxane or a mixture of an alcohol of 5 to50 carbon atoms and an alkali metal alkoxide or a mixture of water and astrong inorganic base, wherein every R is independently phenyl oralkyl-of 1-to-4 carbon atoms, R¹ is H or R, one of R² and R³ is H andthe other is CH₃ and wherein m is from 1 to 8, preferably 1, x is from 2to 40, y is from 0 to 10, and z is from 0 to
 10. 2. A compositionaccording to claim 1, wherein the chain of the organopolysiloxane usedfor the reaction additionally contains units of the formula —Si(R₂)—O—,where R is as defined in claim
 1. 3. A composition according to claim 1or 2, wherein the chain of the organopolysiloxane used for the reactionadditionally contains units of the formula —Si(R)(R⁴)—O—, where R is asdefined in claim 1 and R⁴ is linear or branched alkyl of 5 to 25 carbonatoms.
 4. A composition according to one or more of claims 1 to 3,wherein every R is CH₃.
 5. A composition according to one or more ofclaims 1 to 4, wherein after the reaction of the organopolysiloxane witha compound of the formula (I) water and a strong inorganic base areadded in such an amount that the resultant mixture has a pH in the rangefrom 7.5 to 10.5.
 6. A composition according to one or more of claims 1to 5, wherein the addition of base or of water and acid is followed bythe addition of water and optionally also a dispersant or dispersantmixture in such an amount that an aqueous polysiloxane dispersion isformed.
 7. A composition according to one or more of claims 1 to 6,wherein the strong inorganic base used is sodium hydroxide or potassiumhydroxide.
 8. A composition according to one or more of claims 1 to 7,wherein 20 to 100% of the silicon atoms in the organopolysiloxane usedfor the reaction, except for the two silicon atoms at the chain ends,each have a hydrogen atom attached to them.
 9. A composition accordingto one or more of claims 1 to 8, wherein the organopolysiloxane used forthe reaction contains 10 to 500 silicon atoms.
 10. A compositionaccording to one or more of claims 1 to 9, wherein theorganopolysiloxane used is reacted with a compound of the formula (II)before or simultaneously with the reaction with the compound of theformula (I), or, after the reaction of the organopolysiloxane with thecompound of formula (I), the resultant product is reacted with acompound of formula (II) prior to addition of water and acid or base,this reaction with a compound of formula (II) being carried out in sucha way that the resultant product still contains Si—H bonds,CH₂═C(R¹)—R⁵—X_(b)—R⁶—R_(F)  (II) where R_(F) is a linear or branchedperfluoroalkyl radical of 2 to 20 carbon atoms, X is —O—, —S—, —S—S—,—NR¹—SO₂—, —NR¹—, —NH—CO—O—, —NH—CO—NH—, O—CO— or —CO—O—, R⁶ is CH₂₆,where a is from 0 to 10, R⁵ is R⁶ or an R⁶ radical where a is from 1 to10 and in which a hydrogen atom is replaced by —X_(b)—R⁶—R_(F) or by—COOH, b is 0 or 1, and R₁ is as defined in claim
 1. 11. A compositionaccording to one or more of claims 1 to 10, wherein the reaction iscarried out with such amounts of organopolysiloxane that a total of 0.7to 1.0 C═C double bonds in the compound of the formula (I) and of theformula (II) are used per Si—H bond in the organopolysiloxane.
 12. Acomposition according to one or more of claims 1 to 11, wherein theproduct obtained after the addition of base or of water and acid isreacted with an aminodialkoxyalkylsilane or with a mixture whichincludes such a silane and either a linearα,ω-dihydroxypolyorganosiloxane or a cyclic oligodialkylsiloxane.
 13. Amethod of using a composition according to one or more of claims 1 to 12for treating fiber materials.
 14. A method according to claim 13,wherein the fiber materials are textile fabrics in the form of wovens,knits or nonwovens.